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Creators/Authors contains: "Bin_Rusayyis, Mohammed A"

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  1. One method to improve the properties of covalent adaptable networks (CANs) is to reinforce them with a fraction of permanent cross‐links without sacrificing their (re)processability. Here, a simple method to synthesize poly(n‐hexyl methacrylate) (PHMA) and poly(n‐lauryl methacrylate) (PLMA) networks containing static dialkyl disulfide cross‐links (utilizing bis(2‐methacryloyl)oxyethyl disulfide, or DSDMA, as a permanent cross‐linker) and dynamic dialkylamino sulfur‐sulfur cross‐links (utilizing BiTEMPS methacrylate as a dissociative dynamic covalent cross‐linker) is presented. The robustness and (re)processability of the CANs are demonstrated, including the full recovery of cross‐link density after recycling. The authors also investigate the effect of static cross‐link content on the stress relaxation responses of the CANs with and without percolated, static cross‐links. As PHMA and PLMA have very different activation energies of their respective cooperative segmental mobilities, it is shown that the dissociative CANs without percolated, static cross‐links have activation energies of stress relaxation that are dominated by the dissociation of BiTEMPS methacrylate cross‐links rather than by the cooperative relaxations of backbone segments, i.e., the alpha relaxation. In CANs with percolated, static cross‐links, the segmental relaxation of side chains, i.e., the beta relaxation, is critical in allowing for large‐scale stress relaxation and governs their activation energies of stress relaxation. 
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